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LANGMUIR · 2019 · IF 3.683

Preparation and Application of CO2-Triggered Switchable Solvents in Separation of Toluene/n-Heptane

Zidong Zhang,Yuming Tu,Hui Yu,Weidong Liu,Zhiyong Zhou,Zhongqi Ren

Extraction is a common approach to separating aromatics and alkanes, but solvent recovery remains an issue. The polarity, hydrophobic/hydrophilic balance, and other properties of switchable solvents can be reversibly changed in the presence of various triggers, and taking advantage of this property can greatly simplify the process of solvent recovery. In this work, quaternation and anion exchange were used to prepare several switchable solvents by introducing OH– ions to derivatives of the amidine compound 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The resulting compounds exhibited reversible switching in response to exposure to CO2. Using toluene/n-heptane as a model hydrocarbon mixture, a reversible phase change extraction process was established. Among the four switchable solvents prepared, [C2DBU]OH showed the highest selectivity value and so was used to investigate the effect of various parameters on hydrocarbon separation. The extraction process was found to rapidly reach equilibrium when a two-phase system was generated by bubbling CO2 through the extraction mixture. Increasing the proportion of the solvent increased the selectivity for toluene, while a 1:1 ratio between the solvent and the toluene/n-heptane mixture enhanced the extraction. Increasing the initial toluene concentration reduced the selectivity for toluene, with a value of 5.97 at a toluene concentration of 20%. The switchable solvent recovered its initial state when heated at 60 °C for 1 h. Upon being reused after removal of CO2, the solvent exhibited poor separation characteristics, although the selectivity coefficient remained constant at approximately 3.1 during 10 regenerations. Finally, the mechanism of the switchable solvent effect and modeling of experimental data were investigated.

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CHEMICAL ENGINEERING JOURNAL · 2019 · IF 8.355

Fabrication of Janus graphene oxide hybrid nanosheets by Pickering emulsion template for self-healing nanocomposite hydrogels

Anyao Ma,Guanglin Wang,Zhenglong Yang,Liangjiu Bai,Hou Chen,Wenxiang Wang,Huawei Yang,Donglei Wei,Lixia Yang

Janus nanomaterials can be highlighted to design a series of smart materials with the remarkable characteristic of two different properties or constituents. In this manuscript, functional Janus graphene oxide-type (GO-type) nanomaterials were fabricated by Pickering emulsion template and successfully applied to develop of dual self-healing nanocomposite hydrogels. Asymmetric functionalization of Janus nanosheets were achieved in typical oil-in-water Pickering emulsion by atom transfer radical polymerization (ATRP) and mussel-inspired chemistry. Poly(2-(acryloyloxy)ethyl ferrocenecarboxylate) (PMAEFc) and polydopamine (PDA) were unsymmetrically grafted on the two sides of GO (Janus GO-PMAEF/PDA (JGNs)), which successfully applied in self-healing nanocomposite hydrogels. The collaborative effect of metal-ligand coordination and host-guest interaction make the dual self-healing hydrogels have excellent self-healing properties (self-healing efficiency can reach to 93.4% within 1 h) and mechanical strength (tensile strength of 0.94 MPa and strain of 508.5%). Therefore, these chemical asymmetric JGNs have outstandingly application prospect in the development of smart materials.

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JOURNAL OF ETHNOPHARMACOLOGY · 2019 · IF 3.414

Integrated metallomic and metabolomic profiling of plasma and tissues provides deep insights into the protective effect of raw and salt-processed Achyranthes bidentata Blume extract in ovariectomia rats

Yi Tao,Surun Huang,Jizhong Yan,Weidong Li,Baochang Cai

Ethnopharmacological relevance Achyranthes bidentata Blume (AB) is a well-known traditional Chinese medicine for treating osteoporosis and bone fracture. In the current, researches on pharmacological mechanism of AB mostly focused on molecular pathways, knowledge about its metabolic signatures is largely unclear. This study aims to develop an integrative metabolomics and metallomic approach for deciphering the biochemical basis of anti-osteoporosis effects of raw and salt-processed AB. Method Gas chromatography–mass spectrometry (GC–MS) and inductively coupled plasma mass spectrometry (ICP-MS) were combined for metabolomic and metallomic profiling of rats serum, liver and kidney derived from the sham group, model group, E2, raw and salt-processed AB treated groups. Meanwhile, micro-CT and biomechanical analysis were carried out to ensure the success of the osteoporosis model and to validate the anti-osteoporosis effect of raw and salt-processed AB. Partial least squares discriminant analysis (PLS-DA) was employed to screen potential biomarkers and the MetaboAnalyst and KEGG PATHWAY Database were used to investigate the metabolic pathway. Results Raw and salt-processed AB protected the rats against osteoporosis, as evidenced by the restoration of the alkaline phosphatase activity, osteocalcin concentration, urine calcium/creatinine ratio and urine phosphorus/creatinine ratio. The combination of PCA and PLS-DA revealed deviations in ninety-four differential biomarkers between raw AB treated group and model group. The identified biomarkers were primarily engaged in the metabolic pathways including galactose metabolism, urea cycle, arginine and proline metabolism, alanine metabolism, lactose degradation, ammonia recycling and glycine and serine metabolism. The levels of these biomarkers showed significant alterations and a tendency to be restored to normal values in raw and salt-processed AB treated osteoporosis rats. Of note, the levels of trace elements, such as Zn, Se, Mn, Cu and Fe, were elevated after raw and salt-processed AB treatment. Finally, a correlation network diagram was constructed to show the biomarkers perturbed by raw and salt-processed AB. Conclusion Our findings indicate that raw and salt-processed AB has positive effects on osteoporosis rats. Meanwhile, metabolomic and metallomic method coupled with metabolites enrichment analysis and pattern recognition serves as a useful tool for revealing the action mechanism of traditional Chinese medicine.

CAS / MDL: 142-82-5
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ELECTROPHORESIS · 2019 · IF 2.754

In situ fabrication of microporous organic network coated capillary column for high resolution gas chromatographic separation of hydrocarbons

Yuan-Yuan Cui,Huan Yao,Cheng-Xiong Yang,Xiu-Ping Yan

Microporous organic networks (MONs) are a new class of porous materials synthesized via Sonogashira coupling reactions between organic building blocks. Here we report an in situ synthesis approach to fabricate MONs coated capillary column for high resolution GC separation of hydrocarbons. The McReynolds constant evaluation reveals the MONs coated capillary is a non-polar column. The MONs coated capillary column shows good resolution for GC separation of diverse important industrial hydrocarbons such as linear and branched alkanes, alkylbenzenes, pinene isomers, ethylbenzene and styrene, cyclohexane and benzene. The MONs coated capillary column gave a high column efficiency of 1542 plates per meter for hexane and good precision for replicate separations of the selected hydrocarbons with the RSDs of 0.2–0.3, 1.5–3.1, and 1.9–3.3% for retention time, peak height and peak area, respectively. The MONs coated capillary also offered better resolution than commercial Inert Cap-1 and Inert Cap-5 capillary columns for hexane and heptane isomers. These results reveal the potential of MONs as novel stationary phases in GC.

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JOURNAL OF CHEMICAL THERMODYNAMICS · 2019 · IF 2.29

Isobaric vapor–liquid equilibrium of three binary systems containing dimethyl succinate, dimethyl glutarate and dimethyl adipate at 2, 5.2 and 8.3 kPa

Honglin Chen,Lei Zhang,Yulan Huang,Jingjing Lu,Zhijian Zhao,Xunqiu Wang

The isobaric vapor–liquid equilibrium (VLE) data for three binary systems of dimethyl succinate (DMS) + dimethyl glutarate (DMG), dimethyl succinate +  dimethyl adipate (DMA) and dimethyl glutarate + dimethyl adipate were determined at 2, 5.2 and 8.3 kPa with a dynamic recirculating apparatus and the temperature ranged from 363.39 to 422.4 K. All the experimental data were verified to be thermodynamically consistent according to the Herington method and point to point method of Van Ness test. Afterwards, the VLE data were correlated with Nonrandom two-liquid (NRTL), Wilson and UNIQUAC activity coefficient models, and the interaction parameters of thermodynamic models of these three binary systems were obtained. The results indicated that the calculated values of these three models agreed well with the experimental data, while the NRTL model and UNIQUAC model provided a slightly better result than Wilson model. The calculated root mean square deviations of NRTL model for the temperature and vapor-phase mole fraction were less than 0.13 K, and 0.0023, respectively.

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GREEN CHEMISTRY · 2019 ·Vol. 21 ·期 9 ·2412-2427 · IF 9.405

Modulation of starch nanoparticle surface characteristics for the facile construction of recyclable Pickering interfacial enzymatic catalysis

Liang Qi,Zhigang Luo,Xuanxuan Lu

In this work, maize starch (MS) was successively modified via an esterification reaction with acetic anhydride (AA) and phthalic anhydride (PTA). Combined with the gelatinization–precipitation process, the formed starch nanoparticles at an AA/PTA ratio of 2 (MS-AP (2)) and 3 (MS-AP (3)) had similar regular spheres but distinct surface characteristics. In order to enhance the activity of lipase B from Candida antarctica (CALB) in an organic solvent, we designed an oil-in-water (o/w) and a water-in-oil (w/o) Pickering interfacial catalytic system simultaneously by utilizing MS-AP (2) and MS-AP (3) as robust Pickering emulsion stabilizers. Impressively, during the esterification of 1-butanol and vinyl acetate, the specific activity of CALB in the o/w (0.0843 U μL−1) or w/o (0.0724 U μL−1) Pickering interfacial catalytic system was much higher than that of free enzymes in the monophasic (0.0198 U μL−1) and biphasic (0.0282 U μL−1) system. Moreover, after preliminarily elaborating mass transfer discrepancies between the o/w and w/o Pickering interfacial catalytic systems and calculating their mass transfer resistance, we clarified the effects of the location of these two phases on the catalytic capacity of the Pickering emulsion. Impressively, both Pickering interfacial catalytic systems exhibited high effectiveness in product separation. It was found that the w/o Pickering emulsion enabled the organic product to be facilely isolated through a simple decantation, while the o/w Pickering emulsion achieved similar results after adjusting the system temperature. The bio-based nanomaterials and simple protocol, in conjunction with the stability to simultaneously achieve high catalysis efficiency and excellent recyclability, makes us believe that this starch nanoparticle-based Pickering interfacial catalytic system is a promising system for meeting the requirements of green and sustainable chemistry.

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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2019 · IF 3.131

Effect of number of oxypropylene on dynamic interfacial tensions of extended surfactants

Mengdie Lv,Cong Luo,Jian Yang,Yawen Zhou,Changyao Liu,Baocai Xu

Effect of the numbers of oxypropylene on dynamic interfacial tensions (IFT) of five extended surfactants C 12-14 P m E 2 S (m = 0, 3, 5, 8 and 12) were investigated. The effects of electrolyte (NaCl and CaCl 2 ) concentration, salinity, surfactant concentration were studied in detail. The IFTs between C 12-14 P m E 2 S aqueous solutions and n-decane obtained ultralow range at optimum NaCl concentration expect C 12-14 E 2 S. The optimum salinity (S * ) decreased with increase of number of oxypropylene. Also, the IFTs of C 12-14 P 8 E 2 S and C 12-14 P 12 E 2 S approached or obtained ultralow IFT in a wide range of CaCl 2 concentrations. The IFTs between C 12-14 P 12 E 2 S aqueous solution and n-decane decreased as salinity increased. With increasing surfactant concentration, the values of IFT decreased initially and then increased.

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ACS Sustainable Chemistry & Engineering · 2019 · IF 6.97

Enhancement of CO2 Desorption from a Novel Absorbent (Dimethyl Carbonate) by Using a PDMS/TiO2 Pervaporation Membrane

Ebrahim Ataeivarjovi,Zhigang Tang,Jian Chen,Zhijun Zhao,Guo Dong

Currently, there is strong interest in carbon capture and absorption as a means of reducing carbon dioxide emissions and combating climate change. Unfortunately, the current and traditional methods to achieve such goals are not economical, because they require a huge absorption–desorption plant with high investment and operating costs and high recycle rates of chemical absorbers. In this paper, we propose a novel CO2 capture method combining dimethyl carbonate as a physical solvent and polydimethylsiloxane (PDMS)/TiO2 nanocomposite as a desorption membrane. The effects of TiO2 concentration, feed temperature, and permeate pressure on the pervaporation process for CO2 capture were studied. Results showed that the addition of TiO2 nanoparticles (up to 5 wt %) resulted in 3.61 kg/m2·h flux and 44.68 selectivity of the membrane. The presence of TiO2 nanoparticles in the PDMS membrane not only increased the performance of membrane’s but also reduced (about 72%) energy consumption. To corroborate our experimental findings, a simple simulation was conducted by Gaussian 09. The modeling results demonstrated that the incorporation of TiO2 nanoparticles to the PDMS led to favorable absorption of CO2 compared with the composite one. These results indicate a novel and promising method to capture CO2 effectively and economically for industrial purposes.

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Journal of Cleaner Production · 2019 · IF 6.395

Towards zero-consumption of acid and alkali recycling rare earths from scraps: A precipitation-stripping-saponification extraction strategy using CYANEX®572

Fujian Li,Yanliang Wang,Xiang Su,Xiaoqi Sun

Recycling schemes from rare-earth-containing scraps have been developed rapidly due to the increasing supply risk for rare-earth elements (REEs). This article aimed to reduce the ecological impact and reagent costs for separating and recycling REEs from scraps, i.e., spent ceria-based polishing powders and lutetium-based crystal waste. A simultaneous process was proposed using an industrial extractant Cyanex ® 572, which allowed efficient recycling of REEs from the wastes with less acid and alkali consumption than traditional hydrometallurgy process. Based on thermodynamic and kinetic analyses, common acid scrubbing was avoided by employing REEs scrubbing. Additionally, the alkali saponification, acid stripping and oxalic acid precipitation were substituted by one step of precipitation-stripping-saponification with ammonium fluoride which contained abundant F − in the solution with weak acidity. F − was easy to complex with REEs on the extractant as precipitate while NH 4 + bonded with anion of the extractant. Using this technique, the vast consumption of chemicals and million tons of wastewater in REEs industry may be avoided. Totally, the chemical consumption could be reduced over 80% and the wastewater was decreased more than 90%. REEs recovery yield also increased considerably using the novel process. Moreover, the ammonium fluoride was designed in containment system and was reused with no emission to the environment. This article provides a sustainable and efficient alternative process to REEs waste treatment industry.

CAS / MDL: 142-82-5
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APPLIED CATALYSIS A-GENERAL · 2020 · IF 5.006

Silica/titania composite-supported NiCo catalysts with combined catalytic effects for phenol hydrogenation under fast and mild conditions

Yucheng Li,Jing Liu,Jing He,Luying Wang,Jiandu Lei

The effect of titanium as a promoter for the nickel-cobalt/silica-titania (NiCo/Si-Ti) catalyst in the hydrogenation of phenol was comparatively studied. In the phenol hydrogenation under mild reaction conditions (1 MPa H 2 pressure and 100 °C), the Ti-promoter induces the formation of the Co δ− −O V −Ti 3+ active sites and enhances the hydrogenation activity of the NiCo/Si catalyst to convert phenol to cyclohexanol. The catalytic hydrogenation with the optimal composition of the NiCo/Si-1.0Ti (Si:Ti ratio of 8.5:1) catalyst was completed within 1 h (conversion 98.2 % and selectivity >99 %), which was more efficiently than that with other Ti-doped catalysts and NiCo/Si as baseline, indicating a strong positive synergistic effect between the metal (Ni-Co) and support (Ti-Si) components of the catalyst in this reaction. Additionally, the kinetics, pathway and catalytic mechanism of the hydrogenation of phenol are also examined. Furthermore, the NiCo/Si-1.0Ti catalysts also showed a good performance at reducing the unstable oxygenated compounds in the bio-oil.

CAS / MDL: 142-82-5
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JOURNAL OF CHEMICAL AND ENGINEERING DATA · 2019 · IF 2.298

Measurement and Thermodynamic Modeling of Ternary (Liquid + Liquid) Equilibrium for Extraction of Phenols from Alkane with Furfural

Wenyang Fan,Houchun Yan,Xin Huang,Zhaohui Liao,Qingsong Li,Zhanhua Ma

The extraction process as a kind of energy-saving and environmental protection technology can be used to separate phenols from low-temperature coal tar. The liquid–liquid equilibrium (LLE) data regarding ternary systems n-heptane + phenols + furfural were determined experimentally at 303.2, 323.2, and 343.2 K under the atmospheric pressure condition, where phenols refer to phenol, p-cresol, and 2,6-xylenol. The solvent extraction capacity was assessed by the solute distribution coefficient and selectivity. Othmer–Tobias and Bachman equations were utilized to validate the consistency of the measured data, which the linear correlation (R2) ≥ 0.99. Experimental LLE data were correlated utilizing the NRTL and UNIQUAC thermodynamic models with all of the RMSD and AARD values below 0.01, meaning that each ternary system is satisfactorily in agreement at temperatures studied and the NRTL model gives better agreement than the UNIQUAC model for ternary systems.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2019 · IF 5.107

Extraction of aromatics from aliphatics using a hydrophobic dicationic ionic liquid adjusted with small-content water

Congfei Yao,Yucui Hou,Ying Sun,Weize Wu,Shuhang Ren,Hui Liu

The extraction of aromatics from aliphatics with both high distribution coefficient ( D ) and high selectivity ( S ) is a challenge in the industry. Hydrophobic dicationic ionic liquids (DILs) were demonstrated as efficient extractants with both high D and high S . However, the high viscosity of the DILs may influence their application. In this work, we found that a hydrophobic DIL ([C 5 (MIM) 2 ][NTf 2 ] 2 ) could dissolve a small amount of water with a solubility of 2.24 wt% at 303.15 K. The viscosity and density of the DIL with different contents of water were investigated from 293.15 K to 333.15 K. A small amount of water in the DIL could decrease its viscosity greatly, while had little effect on its density. The effect of water content in the DIL on the extraction performance was studied, and it was found that both D and S remained high when a small amount of water dissolved in the DIL. The highest selectivity and distribution coefficient for toluene were 45.7, 0.86 (water content: 1.10 wt%) and 41.5, 0.75 (water content: 1.59 wt%), respectively. With increasing the carbon chain of aliphatics, both D tol and D ali decreased, but S increased in the presence of water. All the results indicated that the DIL with a small amount of water not only had high D and S simultaneously, but also enhanced the extraction process. Importantly, the use of water in the extraction process accords with the concept of green chemistry.

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